CN111032832B

CN111032832B - Slurry hydrocracking process using a catalyst containing diaspore alumina

Info

Publication number: CN111032832B
Application number: CN201880054805.0A
Authority: CN
Inventors: 佛瑞德·G·索尔伯格; 蓬·T·M·多; 阿拉卡纳达·巴特查里亚; 兰斯·A·贝尔德
Original assignee: UOP LLC
Current assignee: Honeywell UOP LLC
Priority date: 2017-08-24
Filing date: 2018-08-21
Publication date: 2022-07-05
Anticipated expiration: 2038-08-21
Also published as: CN111032832A; US10703990B2; US20190062647A1; WO2019040536A1

Abstract

A method of using an iron oxide and alumina catalyst in SHC having no more than 55 wt% alumina in either a diaspore phase or an alpha phase is disclosed. Alpha alumina is an effective catalyst component for slurry hydrocracking in terms of tio conversion. The drying process should avoid more than 51 wt% of the alumina becoming alpha phase. SHC catalysts are used to convert heavy hydrocarbon feeds into lighter hydrocarbon products.

Description

Slurry hydrocracking process using a catalyst comprising diaspore alumina

Priority declaration

This application claims priority from us application No. 15/685389 filed 24/8/2017, the contents of which are hereby incorporated by reference in their entirety.

Background

The art relates to processes for treating crude oil, and more particularly to hydroconverting heavy hydrocarbons in the presence of a catalyst to provide useful products and further to prepare feedstocks for further refining.

As reserves of conventional crude oil decline, heavy oil must be upgraded to meet the world's demand for transportation fuels. In heavy oil upgrading, the heavier materials are converted to lighter fractions and most of the sulfur, nitrogen and metals must be removed. Heavy oils contain a large proportion of materials with boiling points above 524 ℃ (or 975 ° F) or higher. These heavy hydrocarbon feedstocks can be characterized by low reactivity in visbreaking, high coking tendency, difficulty in hydrocracking, and distillation difficulties. Most residual oil feedstocks to be upgraded contain a content of asphaltenes, which are generally understood to be high molecular weight compounds that are insoluble in heptane but soluble in toluene, as determined by ASTM D3279 or ASTM D6560. It has now been found that a Slurry Hydrocracking (SHC) process achieves high liquid yields by using catalyst fines while substantially reducing coke formation.

In SHC, a three-phase mixture of a liquid heavy oil feed produces lighter products at elevated temperature and pressure in the presence of gaseous hydrogen over a solid catalyst. Iron Sulfate Monohydrate (ISM) is a conventional SHC catalyst. The ISM was sulfided in the reactor to the active phase-pyrrhotite.

Bauxite and laterite have been disclosed as effective SHC catalysts. These naturally occurring minerals can be milled to smaller sizes to better disperse and facilitate mass transfer. Iron can be an effective SHC catalyst when it is contained in the bauxite or laterite as a sulfide (as pyrrhotite).

Toluene can be used as a solvent to dissolve and separate the carbon-containing solids from the lighter hydrocarbons in the SHC product. The toluene-insoluble solid comprises the catalyst and toluene-insoluble organic residue (TIOR). The TIOR includes coke and a mesophase, and is heavier and less soluble than bitumen. The formation of the mesophase is a critical reaction constraint in slurry hydrocracking reactions. The mesophase is a semi-crystalline carbonaceous material defined as round anisotropic particles boiling above 524 ℃ in pitch. The presence of the mesophase may serve as a warning to indicate that the operating conditions in the SHC reactor are too severe and that coke formation may occur under the prevailing conditions.

As the number and volume of SHC operations used to upgrade heavy oil increases, more efficient SHC catalyst needs to be supplied. Since ISM is continuously added to the process and lost in unconverted bitumen, there is a need for a more active catalyst species that can be added at lower concentrations while providing comparable hydrogenation and mesophase inhibition compared to ISM.

Disclosure of Invention

We have found that diaspore alumina is a less effective catalyst component for slurry hydrocracking in terms of tio conversion. Measures should be taken to avoid the use of iron oxide and alumina minerals having more than 55 wt% of alumina in the diaspore phase, or to avoid converting the alumina in the iron oxide and alumina minerals to more than 51 wt% of alpha phase, in order to maintain the effectiveness of the SHC catalyst. The drying process should avoid conversion of the alumina to more than 51 wt% alpha phase.

Definition of

The term "communicate" means operatively permitting the flow of a substance between enumerated components.

The term "downstream communication" means that at least a portion of a substance flowing to the body in downstream communication can operatively flow from an object with which it is in communication.

The term "upstream communication" means that at least a portion of the substance flowing from the body in upstream communication can operatively flow to the object in communication therewith.

The term "column" means one or more distillation columns for separating one or more components of different volatility. Unless otherwise specified, each column includes a condenser at the top of the column for condensing a portion of the top stream and refluxing it back to the top of the column, and a reboiler at the bottom of the column for vaporizing a portion of the bottom stream and returning it to the bottom of the column. The feed to the column may be preheated. The top pressure is the pressure of the vapor overhead at the vapor outlet of the column. The bottom temperature is the liquid bottom outlet temperature. Overhead and bottoms lines refer to the net lines to the column from any column downstream of reflux or reboil. The stripping column may omit a reboiler at the bottom of the column and instead provide the heating requirements and separation power for the inert fluid (such as steam). The stripper is typically fed from a top tray and the main product is withdrawn from the bottom.

As used herein, the term "boiling point temperature" means the Atmospheric Equivalent Boiling Point (AEBP) calculated from the Observed boiling temperature and distillation pressure, as calculated using the formula provided in ASTM D1160 appendix a7 "the Practice of Converting the Observed Vapor temperature to Atmospheric Equivalent temperature" (Practice for Converting the Observed Vapor temperature to an Atmospheric Equivalent temperature).

As used herein, the term "true boiling point" (TBP) means a test method corresponding to ASTM D-2892 for determining the boiling point of a material used to produce standardized masses of liquefied gases, fractions and residues from which analytical data can be obtained, and determining the yields of such fractions by both mass and volume from which a plot of distillation temperature versus mass% is obtained in a column having a reflux ratio of 5: 1 using 15 theoretical plates.

As used herein, "pitch" means a hydrocarbon material that boils above 524 ℃ (975 ° F) AEBP as determined by any standard gas chromatography simulated distillation method, such as ASTM D2887, D6352, or D7169 (all of which are used by the petroleum industry).

As used herein, the term "T5" or "T95" means the temperature at which a sample, as determined using ASTM D-86, boils 5 volume percent or 95 volume percent, respectively (as the case may be).

As used herein, the term "initial boiling point" (IBP) means the temperature at which a sample begins to boil, as determined using ASTM D-86.

As used herein, the term "endpoint" (EP) means the temperature at which the sample is fully boiled using ASTM D-86.

As used herein, the term "diesel boiling range" means that hydrocarbons boil in a range between 204 ℃ (399 ° F) and 343 ℃ (650 ° F) using a TBP distillation process.

As used herein, the term "diesel conversion" means the conversion of a feed boiling above the diesel cut point to a material boiling at or below the diesel cut point in the diesel boiling range.

As used herein, "pitch conversion" means the conversion of material boiling above 524 ℃ (975 ° F) to material boiling at or below 524 ℃ (975 ° F).

As used herein, the term "vacuum gas oil" means a hydrocarbon material that boils in the AEBP range between 343 ℃ (650 ° F) and 524 ℃ (975 ° F), as determined by any standard gas chromatography simulated distillation method, such as ASTM D2887, D6352, or D7169 (all of which are used by the petroleum industry).

As used herein, the term "separator" means a vessel having an inlet and at least one overhead vapor outlet and one bottom liquid outlet, and may also have an outlet for an aqueous stream from a storage tank (boot). A flash drum is a separator that can be in downstream communication with a separator that can operate at higher pressures.

As used herein, the term "predominantly" or "predominantly" means greater than 50%, suitably greater than 75%, and preferably greater than 90%.

As used herein, solvent "insoluble" means a material that is not soluble in the solvent.

Description of the invention

Iron oxide and aluminum oxide mineral catalysts are effective for SHC. The mineral catalyst fines are mixed with a heavy hydrocarbon liquid feed and hydrogen to form a heavy hydrocarbon slurry comprising hydrocarbon liquid, hydrogen and catalyst fines. In the SHC reactor, the heavy hydrocarbons in the slurry are cracked in the presence of hydrogen and catalyst particles to produce a hydrocracked slurry product comprising lighter hydrocarbon products.

Typical iron oxide and aluminum oxide minerals include laterites and bauxites. Red mud, alumina depleted bauxite, may also be used as an SHC catalyst. Although it has been shown that iron oxides and hydroxides present in bauxite and laterites undergo sulfidation during SHC to produce pyrrhotite to form an active hydrogenation catalyst, some bauxite and laterite samples with high iron content do not provide sufficient SHC activity. Use of XRD on hematite (Fe)₂O₃) Estimates of the average crystallite size indicate that there is not much difference in the dispersion of iron oxide in the bauxite samples between good and poor performance. We have found that dried iron oxide and aluminium oxide minerals with alpha phase aluminium oxide and a process for their preparationMaterials with other phases of alumina (such as chi or gamma) are less efficient SHC catalysts than materials with other phases. Alpha alumina is a low surface area phase which results in low activity for slurry hydrocracking.

An effective mineral for SHC catalysts comprises between 2 and 80 wt% iron oxide and between 20 and 98 wt% alumina. Alumina may occur naturally in iron oxide and alumina minerals, which are typically present in the form of boehmite, gibbsite or diaspore. The alumina may be provided to the catalyst by derivatives such as spinels and perovskites. The alumina in the mineral particles may constitute between 20 and 98 wt%, typically not more than 95 wt% of the particles, and preferably between 50 and 84 wt% of the particles.

We have determined that iron oxide and alumina minerals can be effective SHC catalysts as long as no more than 51 wt% of the alumina in the particles is in the alpha phase. We have found that 3 wt% ISM can provide at least 80 wt% bitumen conversion and no more than 3.1 wt% TIOR yield in the heavy hydrocarbon feed added to the SHC reactor. We conclude that 1.5 wt.% of iron oxide and alumina minerals having no more than 55 wt.% alpha phase alumina can also provide a bitumen conversion of at least 80 wt.% and a TIOR yield of no more than 3.1 wt.%.

The most common naturally occurring alumina phases in minerals are boehmite, gibbsite and diaspore. The chemical formula of the gibbsite is Al (OH)₃. At temperatures less than 275 ℃, gibbsite may be partially dehydrated to boehmite or completely dehydrated to chi alumina. Chi alumina can be converted to kappa and then to alpha, but does not undergo conversion to alpha at less than 1000 ℃. Boehmite has the formula alo (oh), where most of the water is in the amorphous phase. Boehmite can be converted to gamma alumina at 300 ℃ to 500 ℃. The gamma alumina can then be converted to the delta, theta and alpha phases in sequence, but not to alpha at less than 1000 ℃. The chemical formula of diaspore aluminum oxide is AlO (OH); unlike boehmite, however, diaspore alumina has water in the crystalline phase. Gibbsite is converted to alpha alumina at relatively low temperatures between 400 ℃ and 500 ℃。

We have found that the dehydrated iron oxide and alumina minerals are also more effective SHC catalysts and preferably dried before mixing them with the heavy hydrocarbon liquid feed. The alumina in the iron oxide and alumina catalyst particles should contain less than 15 wt% water, and preferably typically contains less than 10 wt% water after some degree of drying. If the iron oxide and aluminum oxide mineral particles are heat treated to provide chi and/or gamma phase aluminum oxide, the iron oxide and aluminum oxide mineral particles may have less than 1 wt.% water. The dried alumina is typically converted to the gamma or chi phase, having a greater surface area than before drying, thereby increasing the catalytic activity of the mineral. Drying also facilitates grinding to finer particles, and removal of water concentrates the catalytically active components in the mineral particles, which improves transport capacity and reduces the required catalyst addition rate.

Drying may be achieved by heat treatment to remove water and other volatiles from the mineral. The volatiles can be removed by evaporating the mineral particles in the unconverted state. Some volatiles may be generated by chemical reactions of the non-volatile components of the mineral, which may be energized by heating to produce volatiles that may subsequently be evaporated. The heat treatment may also effect phase transfer of the alumina to other phases. The heat treatment may include calcination, roasting, drying, dewatering and any method of heating the mineral particles to an elevated temperature, preferably above 150 ℃. In one aspect, the heat treatment is achieved by: a gas such as air is flowed over the iron oxide and aluminum oxide mineral particles in the furnace heated to the target temperature for a sufficient time, such as 2-50 hours, to bring the minerals to the target heat treatment temperature.

Providing iron oxide and aluminum oxide particles having no more than 51 wt.% of aluminum oxide in the alpha phase in the particles can be accomplished by: ensuring that the mineral particles have no more than 55 wt% gibbsite phase alumina. The iron oxide and alumina particles may have at least 0.5 wt.% gibbsite phase alumina. Suitably, the iron oxide and aluminium oxide particles may have at least 1 wt% or at least 5 wt% gibbsite phase aluminium oxide. The alumina in the iron oxide and alumina catalyst particles may comprise at least 40 wt.%, preferably at least 45 wt.% total gibbsite alumina and/or boehmite alumina. If the iron oxide and alumina particles (the mineral particles of which have no more than 55 wt% gibbsite phase alumina or at least 40 wt%, preferably at least 45 wt% total gibbsite and/or boehmite alumina) are heat treated at no more than 1000 c, preferably no more than 800 c, such as between 150 c and 800 c, the insufficient amount of alumina in the iron oxide and alumina particles will be converted to the alpha phase to provide no more than 51 wt% alpha phase alumina. This assumes that all of the gibbsite is converted to the alpha phase because gibbsite and boehmite will not be converted to the alpha phase in this temperature range. The remaining non-diaspore phase alumina in the iron oxide and alumina mineral particles will typically be in the gibbsite or boehmite phases.

If the iron oxide and alumina particles (the mineral particles of which have no more than 55 wt% gibbsite phase alumina or at least 40 wt% in total, preferably at least 45 wt% gibbsite and/or boehmite alumina) are heat treated at no more than 600 c (such as between 150 c and 600 c), then an insufficient amount of the alumina in the iron oxide and alumina particles will be converted to the alpha phase to provide no more than 51 wt% alpha phase alumina. This is a result of all gibbsite being converted to boehmite or chi phase and all boehmite being converted to gamma phase leaving insufficient boehmite to be converted to alpha phase. chi and gamma phase alumina are catalytically active against SHC. Preferably, at least 45 weight percent of the alumina in the iron oxide and aluminum oxide particles is in the chi and/or gamma phase after the heat treatment, and preferably, at least 49 weight percent of the alumina in the iron oxide and aluminum oxide particles is in the chi and/or gamma phase after the heat treatment.

If the iron oxide and alumina particles comprise more than 55 wt% alumina in the gibbsite phase, they should be dried at no more than 500 ℃, preferably no more than 450 ℃, more preferably no more than 400 ℃, such as between 150 ℃ and 450 ℃ or such as between 150 ℃ and 400 ℃ to avoid transformation of the gibbsite alumina phase to the alpha phase, thereby providing particles with more than 51 wt% alumina in the alpha phase.

The iron oxide and alumina minerals preferably comprise gibbsite or boehmite alumina phases prior to heat treatment. The iron oxide and alumina mineral particles may have at least 25 wt.%, suitably at least 35 wt.%, preferably at least 40 wt.%, most preferably at least 45 wt.%, and more suitably at least 50 wt.% alumina in the gibbsite or boehmite phases prior to heat treatment. The gibbsite and boehmite alumina phases do not convert to alpha alumina phases upon heat treatment to elevated temperatures of 1000 c and suitably 800 c.

The iron oxide and alumina mineral particles typically comprise at least 2 wt%, more typically at least 3 wt%, suitably at least 5 wt%, and preferably at least 10 wt% iron oxide. The iron oxide and alumina mineral particles typically comprise no more than 80 wt% iron oxide, and preferably comprise between 10 wt% and 45 wt% iron oxide. The iron oxide can be hematite, Fe₂O₃Or magnetite, Fe₃O₄Or in the form of a hydrate before heat treatment.

The iron oxide and aluminum oxide particles should contain no more than 30 wt.% diaspore prior to heat treatment. In addition, no more than 26% by weight of the iron oxide and aluminum oxide particles should be in the alpha phase after heat treatment.

Thermogravimetric analysis can be used to quantitatively analyze the weight fraction of hydrated alumina such as diaspore, gibbsite and boehmite in iron oxide and alumina microparticles by specifying the sample weight loss at peak positions under standard conditions, such as in Foldvari's "Handbook of mineral Thermogravimetric analysis systems of Minerals and Its Use in Geological Practice" (2011, budapest). X-ray diffraction quantitative phase analysis using Rietveld refinement according to b.gan, INT' L juournal min.proc.123, p.64-72(2013) can be used to quantitatively analyze the weight fraction of the alumina phase of the heat-treated iron oxide and alumina particles.

Bauxite is the preferred large number of usable minerals having the above proportions. Bauxite typically has 10 to 40 weight percent iron oxide (Fe)₂O₃) And 54 to 84 weight percent alumina, and may have 10 to 35 weight percent iron oxide and 55 to 80 weight percent alumina. Bauxite may also contain silicon dioxide (SiO)₂) And titanium dioxide (TiO)₂) The total amount thereof generally does not exceed 10% by weight, and the total amount thereof generally does not exceed 6% by weight. Suitable bauxite is purchased from saint goban haydite located in smith burgh, arkansas.

Laterites are another suitable iron and aluminum oxide mineral for SHC catalysts.

The best iron oxide and aluminum oxide minerals do not include clays such as kaolinite. Suitably, the iron oxide and aluminium oxide minerals comprise no more than 10 wt% clay, and preferably no more than 5 wt% clay.

Red mud comprising bauxite and in which the majority of the alumina has been extracted will have a higher proportion of iron and a lower proportion of alumina, such as 3 to 30 wt% alumina and preferably 25 to 90 wt% iron oxide, and preferably between 35 and 60 wt% iron oxide. Calcium oxide may be present in the red mud in an amount of 1 to 40% by weight, and preferably between 1 to 10% by weight. The preferred red mud has a small proportion of micropores having a maximum diameter of less than 75 angstroms, such as less than 10%, and preferably less than 5% less than 75 angstroms of its maximum diameter.

Volatiles such as water and carbon dioxide are also present in a large number of available minerals, but the weight proportions described herein above do not include volatiles.

It is also preferred that the iron oxide and aluminum oxide mineral particles are not impregnated with other metals such as molybdenum. However, the iron oxide and aluminum oxide mineral particles may be mixed with other SHC catalyst components such as molybdenum or carbon.

We have found that iron oxide and alumina minerals are the most effective SHC catalysts after they are milled to a smaller particle size, preferably before mixing with the heavy hydrocarbon liquid feed, for the purpose of better dispersion and promotion of mass transfer. The minerals may be ground using a hammer mill, jet mill, ball mill or similar mechanical mill to have an average particle size of between 1 and 50 microns. Suitable average particle sizes are between 1 and 27 microns. The preferred average particle size is between 14 and 19 microns.

The process is capable of converting a substantial portion of a heavy hydrocarbon feedstock to lighter hydrocarbon products. The process is capable of processing aromatic feedstocks as well as feedstocks that have traditionally been very difficult to hydrotreat, such as atmospheric or vacuum residues, visbroken residues, deasphalted bottoms, off-spec bitumen, oil tank bottoms, tar sands, bitumen, and the like. Suitable feeds include atmospheric residue having an IBP greater than or equal to 650 ° F (343 ℃), heavy Vacuum Gas Oil (VGO) having an IBP greater than or equal to 800 ° F (426 ℃) and vacuum residue having an IBP greater than or equal to 950 ° F (510 ℃). A feed having a T90 of greater than or equal to 572 ℃ F. (300 ℃ C.) is suitable. Suitable feeds include API gravities of no more than 20 degrees, typically no more than 10 degrees, and may include feeds having less than 5 degrees.

In an exemplary SHC process, a heavy hydrocarbon oil feed, an optional recycled bitumen stream containing catalyst particulates, and an optional recycled heavy vgo (hvgo) can be combined and heated before being pumped to the inlet of the bottom of a tubular SHC reactor (referred to as a bubble column). The solid mineral particulates of iron oxide and aluminum oxide catalyst may be added directly to the heavy hydrocarbon oil feed in the SHC reactor, or may be mixed with the heavy hydrocarbon oil feed prior to entering the reactor to provide a slurry in the reactor. After heating, the recovered hydrogen and/or make-up hydrogen is fed to the SHC reactor. Both the hydrocarbon oil feed and the hydrogen can be distributed in an SHC reactor with appropriate distributors. Preferably, the recycled pitch stream comprises from 0 to 25 wt% of the feedstock to the SHC reactor, while the HVGO comprises from 0 to 20 wt% of the feedstock, depending on the quality of the feedstock and the single pass conversion level. The feed to the SHC reactor contains three phases, solid catalyst fines, liquid hydrocarbon feed (which may include solid hydrocarbons in the recycle bitumen), and gaseous hydrogen and hydrocarbons.

The process can be operated at moderate pressures in the range of 3.5MPa (500psig) to 24MPa (3500psig), and preferably in the range of 10.3MPa (1500psig) to 19.3MPa (2800psig), without coke formation in the SHC reactor with a suitable catalyst.The reactor temperature is typically in the range of 400 ℃ to 500 ℃, with temperatures of 440 ℃ to 465 ℃ being suitable, and preferably in the range of 425 ℃ to 460 ℃. LHSV, based on fresh feed, is generally below 4h^-1Wherein 0.05h to 1.5h^-1Is preferably in the range of 0.3 to 1h^-1The range of (1) is particularly preferable. Although SHC can be carried out in a variety of known upflow or downflow reactors, it is particularly suitable for bubble column reactors through which feed, catalyst and gases move upwardly. Thus, the outlet of the SHC reactor is higher than the inlet. One or more SHC reactors may be utilized in parallel or in series. As the liquid feed is converted to vapor product, a tendency for foaming occurs in the SHC reactor. An anti-foaming agent may also be added to the SHC reactor, preferably to the top thereof, to reduce the tendency to foam.

A hydrocracking slurry product, which may comprise a gas-liquid mixture, is withdrawn from the top of the SHC reactor. The hydrocracking slurry product may be separated and cooled by a series of separators, stripped of hydrogen sulfide and other gases in a product stripper column, and staged in atmospheric pressure fractionation columns and vacuum columns to provide a product stream. The product fractionator produces a light gas stream recovered in the overhead line, a naphtha product stream from the bottom of the fractionator overhead receiver, a diesel stream, a light VGO stream, a heavy VGO stream, and a bitumen stream from the bottom of the column. The heavy VGO stream can be recycled to the SHC reactor because its high aromaticity can reduce the coking tendency in the reactor. At least some of the pitch stream may also be recycled to the SHC reactor.

The activated iron sulfide in the iron oxide and aluminum oxide catalyst particles has a variety of molecular forms, typically represented by the formula Fe_xS represents, wherein x is between 0.7 and 1.3. We have found that when a mixture of a hydrocarbon and a catalyst is heated to 410 ℃ in the presence of hydrogen and sulphur, substantially all of the iron oxide in the iron oxide and alumina particles (such as bauxite) is converted to iron sulphide. In this connection, "substantially all" means that no iron oxide peak is generated at 2 θ degrees of 33.1 or not less than 99% by weight is converted into iron sulfide on an XRD pattern of intensity with respect to 2 θ degrees. Sulfur can be made intoIs an organic sulfur compound present in the hydrocarbon feed. Thus, the iron in the mineral particles may be in the +3 oxidation state, preferably as Fe₂O₃Added to the heavy hydrocarbon feed.

Examples

Example 1

The catalyst was tested using Urals vacuum residue having the characteristics in Table 1.

TABLE 1

Density, g/cm³	1.013
		Sulfur, wt.%	2.89
Carbon, wt.%	83.1
		Hydrogen, wt.%	10.2
Nitrogen, by weight%	0.34
		Heptane insoluble matter,% by weight	5.78
Carbon residue, wt.%	17.9
		Pentane insolubles, wt%	10
Toluene insolubles,% by weight	0.4

Tests were performed to check the activity of the catalyst. To measure the catalyst activity, the experimental setup was run in batch mode: 1 liter stirred tank autoclave reactor. In a standard activity test for measuring the activity of a conventional ferric sulfate monohydrate (ISM) catalyst, a reactor was charged with 500g of Ural vacuum residue, 2.5g of sulfur powder, and 15g of ISM such that the catalyst comprised 3.0 wt.% of the fresh residue feed. To measure the activity of the iron oxide and aluminum oxide catalysts, the reactor was charged with 500g of Ural vacuum residue, 2.5g of sulfur powder, and 7.5g of bauxite such that the catalyst accounted for 1.5 wt.% of the fresh residue feed.

The reactor was first pressurized to 14MPa (gauge) (2000psig) and pure hydrogen stirred at 1000rpm for batch testing. The reactor was then rapidly heated to 450 ℃ over 15 minutes, held at this temperature for 120 minutes, then rapidly cooled and depressurized. During the test, hydrogen was kept flowing into the reactor through an eductor submerged in liquid at a rate of 6.52 standard liters/minute, which carried the lighter cracked components out of the reactor into a room temperature knock-out pot trap and a downstream cooled knock-out pot trap operating at 4 ℃. The tio yield was calculated as the difference between the toluene insoluble solids and the product liquid ash content. Conversion was calculated by subtracting the ratio of unconverted feed to total feed from one. The unconverted feed is defined as the sum of the tio solids and the portion of the reactor liquid product boiling above 524 ℃ (975 ° F).

For standard activity testing of the residue feed with a 3.0 wt% ISM catalyst concentration, the toluene insoluble organic residue yield (TIOR) was 3.1 wt%. As the ISM was converted to the active catalyst form in the reactor, the ISM lost half of its weight, so bauxite loaded at 1.5 wt% in the residue feed produced approximately the same ash concentration in the bitumen. Although adding more bauxite reduces the TIOR yield, it also results in more ash in the bitumen product, which is quickly unacceptable in terms of process economics.

The properties and results of the bauxite samples tested are shown in table 2.

TABLE 2

Determining the maximum acceptable gibbsite content in naturally occurring minerals is not feasible due to the inability to synthesize natural minerals and obtain meaningful results. Thus, the amount of diaspore that may be present in the mineral mixture if one of these minerals also contains non-diaspore alumina is calculated without allowing a yield above the acceptable TIOR. Using the highest activity diaspore containing bauxite we found: samples 2-953, capable of producing 3.7 wt% TIOR and the highest activity bauxite with either diaspore or alpha alumina; sample a, capable of yielding 2.4 wt% TIOR; the mixture, comprising 53.8 wt% of diaspore containing bauxite from samples 2-953 and 46.2 wt% of bauxite of diaspore or alpha alumina, is expected to provide a 3.1 wt% TIOR yield, equivalent to the TIOR yield of a higher concentration of conventional ISM catalyst:

2.4x+3.7(1-x)＝3.1 (1)

where x is the weight fraction of bauxite that contains no boehmite or alpha alumina.

Because gamma alumina has a larger surface area and a lower water content, it is expected to be a more effective alumina phase for SHC catalysts than gibbsite and boehmite. Furthermore, this makes the catalyst more active on a weight basis, even assuming that the removal of volatile species from the catalyst has no positive effect on the activity from iron.

According to table 2, assuming that all the alumina in samples 2-953 was diaspore phase, samples 2-953 containing diaspore (53.8 wt% of the blended bauxite mineral) contained 25.49 wt% aluminum, corresponding to up to 56.67 wt% diaspore (AlOOH). Thus, the total blend mass would contain 30.49 wt% diaspore:

53.8 wt.% 56.67 wt.% to 30.49 wt.% (2).

If all of the diaspore in sample 2-953 were converted to alpha phase, it would contain 48.16 alpha alumina (Al)₂O₃)。

Sample a, which contained 46.2 wt.% of blended bauxite mineral without boehmite, contained 28.45 wt.% aluminum, corresponding to 53.76 wt.% gamma alumina (Al)₂O₃). Thus, the entire blend mass will contain 24.84 wt.% gamma alumina:

46.2 wt.% 53.76 wt.% 24.84 wt.% (3).

The gibbsite content of the hypothetical blend mass was thus 30.49 wt.% and the gibbsite content of the alumina fraction of the hypothetical blend mass was 55.11 wt.%:

30.49 wt.% (30.49 wt.% +24.84 wt.%) is 55.11 wt.% (4).

If all of the diaspore in the hypothetical blend was heat treated and converted to alpha phase, 25.91 wt% of the total blend would be in alpha phase:

53.8 wt.% 48.16 wt.% 25.91 wt.% (5).

Further, 51.05 wt% of the alumina in the blend mass will be in the alpha phase:

25.91 wt.% (25.91 wt.% +24.84 wt.%) to 51.05 wt.% (6).

Detailed description of the preferred embodiments

While the following is described in conjunction with specific embodiments, it is to be understood that this description is intended to illustrate and not limit the scope of the foregoing description and the appended claims.

A first embodiment of the invention is a process for converting a heavy hydrocarbon feed to lighter hydrocarbon products comprising providing catalyst particles comprising iron oxide and aluminum oxide, said aluminum oxide comprising no more than 55 wt.% diaspore, and said aluminum oxide comprising less than 15 wt.% water; mixing the heavy hydrocarbon liquid feed with hydrogen and the catalyst particulates to form a heavy hydrocarbon slurry comprising hydrocarbon liquid and catalyst particulates; hydrocracking hydrocarbons in the heavy hydrocarbon slurry in a hydrocracking reactor in the presence of the hydrogen and the catalyst particulates to produce a hydrocracking slurry product comprising lighter hydrocarbon products; and withdrawing the hydrocracked slurry product from the hydrocracking reactor. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising heat treating the catalyst particles prior to mixing with the heavy hydrocarbon liquid. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the alumina in the catalyst particulate comprises less than 10 wt% water. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising heat treating the catalyst particles at a temperature between 150 ℃ and 800 ℃. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the alumina in the catalyst particulates comprises at least 40 wt.% gibbsite alumina and/or boehmite alumina. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising heat treating the catalyst particles at a temperature between 150 ℃ and 600 ℃. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the alumina in the catalyst particulate comprises at least 0.5 wt.% diaspore alumina.

A second embodiment of the invention is a process for converting a heavy hydrocarbon feed to lighter hydrocarbon products comprising thermally treating catalyst particles comprising iron oxide and aluminum oxide to provide dried catalyst particles comprising no more than 51 wt.% of said aluminum oxide in the alpha phase; mixing a heavy hydrocarbon liquid feed with hydrogen and dried catalyst particulates to form a heavy hydrocarbon slurry comprising hydrocarbon liquid and catalyst particulates; hydrocracking hydrocarbons in the heavy hydrocarbon slurry in a hydrocracking reactor in the presence of the hydrogen and the catalyst particulates to produce a hydrocracking slurry product comprising lighter hydrocarbon products; and withdrawing the hydrocracked slurry product from the hydrocracking reactor. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the catalyst particulates prior to heat treatment comprise no more than 55 wt.% alumina in a diaspore phase. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising heat treating the catalyst particles at a temperature between 150 ℃ and 800 ℃ to provide dried catalyst particles. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the catalyst particulates prior to heat treatment comprise no more than 30 wt.% alumina in a diaspore phase. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising heat treating the catalyst particles at a temperature between 150 ℃ and 400 ℃. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the catalyst particles prior to the heat treatment comprise at least 40 wt% alumina in a gibbsite phase and/or a boehmite phase. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising heat treating the catalyst particles at a temperature between 150 ℃ and 600 ℃. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the catalyst particulates, after heat treatment, comprise at least 40 wt.% alumina in the chi phase and/or the gamma phase.

A third embodiment of the invention is a process for converting a heavy hydrocarbon feed to lighter hydrocarbon products comprising mixing a heavy hydrocarbon liquid feed with hydrogen and catalyst particulates comprising iron oxide and aluminum oxide to form a heavy hydrocarbon slurry comprising hydrocarbon liquid and catalyst particulates, the aluminum oxide comprising no more than 55 wt.% gibbsite aluminum oxide and at least 40 wt.% gibbsite and/or boehmite aluminum oxide; hydrocracking hydrocarbons in the heavy hydrocarbon slurry in a hydrocracking reactor in the presence of the hydrogen and the catalyst particulates to produce a hydrocracking slurry product comprising lighter hydrocarbon products; and withdrawing the hydrocracked slurry product from the hydrocracking reactor. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the alumina in the catalyst particulate comprises at least 0.5 wt.% diaspore alumina. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph further comprising heat treating the catalyst particles at a temperature of not more than 600 ℃. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the dried catalyst particles comprise no more than 55 wt.% alpha alumina. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the dried catalyst particles comprise at least 45 wt% alumina in the chi phase and/or the gamma phase.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent and can readily ascertain the essential characteristics of the present invention without departing from the spirit and scope thereof, to make various changes and modifications of the invention and to adapt it to various usages and conditions. Accordingly, the foregoing preferred specific embodiments are to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever, and is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

In the foregoing, all temperatures are shown in degrees celsius and all parts and percentages are by weight unless otherwise indicated.

Claims

1. A process for converting a heavy hydrocarbon liquid feed to lighter hydrocarbon products, comprising:

providing catalyst particles comprising iron oxide and aluminum oxide, the aluminum oxide comprising diaspore, wherein the aluminum oxide comprises no more than 55 wt.% diaspore and the aluminum oxide comprises less than 15 wt.% water;

heat treating the catalyst particles to provide dried catalyst particles comprising no more than 51 wt% of the alumina in the alpha phase;

mixing the heavy hydrocarbon liquid feed with hydrogen and the catalyst particulates to form a heavy hydrocarbon slurry comprising hydrocarbon liquid and catalyst particulates;

hydrocracking hydrocarbons in the heavy hydrocarbon slurry in a hydrocracking reactor in the presence of the hydrogen and the catalyst particulates to produce a hydrocracking slurry product comprising lighter hydrocarbon products; and

removing the hydrocracked slurry product from the hydrocracking reactor.

2. The method of claim 1, further comprising thermally treating the catalyst particulates prior to mixing with the heavy hydrocarbon liquid.

3. The method of claim 2, further wherein the alumina in the catalyst particulate comprises less than 10 wt% water.

4. The method of claim 2, further comprising heat treating the catalyst particulate at a temperature between 150 ℃ and 800 ℃.

5. The method of claim 1, wherein the alumina in the catalyst particles comprises at least 40 wt.% gibbsite alumina and/or boehmite alumina.

6. The method of claim 5, further comprising heat treating the catalyst particulate at a temperature between 150 ℃ and 600 ℃.

7. The method of claim 1, wherein the alumina in the catalyst particulate comprises at least 0.5 wt.% diaspore alumina.

8. The method of claim 1, further comprising heat treating the catalyst particles at a temperature between 150 ℃ and 800 ℃ to provide dried catalyst particles.

9. The method of claim 1, wherein the alumina comprises at least 40% by weight gibbsite alumina and/or boehmite alumina.